Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
  • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/06—Preparatory processes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/06—Preparatory processes
  • C08G77/08—Preparatory processes characterised by the catalysts used
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/06—Preparatory processes
  • C08G77/10—Equilibration processes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
  • C08J2383/04—Polysiloxanes

Definitions

• the present invention relates to a process for making stable high viscosity organopolysiloxane emulsion and in particular to an emulsion-polymerisation process involving a simple and cost-effective faster completion of emulsification of organopolysiloxane and also subsequent polymerisation of the organopolysiloxane.
• the process is directed to be simple and cost-effective and can be easily adapted for emulsion production of stable organopolysiloxane emulsions for diverse beneficial end use and application.
• the silicone emulsion produced by the process of the invention is in the range of average (i.e D50 value) up to 150 nanometer with a very narrow particle size distribution which is highly stable and found to have advantageous and beneficial diverse use in various end applications including in personal care, textile -, rubber, paper and other like applications/uses.
• organopolysiloxane emulsions with varying particle sizes to suit different end applications.
• Organopolysiloxane emulsions having low particle size prepared by emulsion polymerisation process are generally preferred which could provide the desired faster and simple production with focus on emulsion stability and quicker organopolysiloxane polymerisation during emulsification.
• Such emulsion polymerised products are known to be prepared by various methods.
• JP-B 34-2041 disclosed a polymerisation process wherein a strong acid and strong base are used as a polymerisation catalyst.
• US 3697469 used ion-exchange resin as polymerisation catalyst.
• US 6245852 discloses a process of preparation of organopolysiloxane emulsion having improved stability within a short time.
• the process comprising the steps of emulsifying and dispersing low molecular weight organopolysiloxane in water in presence of essentially at least one anionic surfactant selected from organic sulphonic acid and organic sulphates by using a high pressure homogeniser with a operating pressure range from 700 to 3000 Kg/cm 2 and produce an initial emulsion having particle size up to 300 nm, followed by allowing the emulsion for polymerisation and subsequent neutralization of the emulsion at the end.
• Emulsion polymerisation process usually consists of emulsification of organopolysiloxane and subsequent polymerisation of the organopolysiloxane. So, faster emulsification on its own is not sufficient to complete emulsion polymerisation process or make the process faster. Therefore, it is also important to make faster polymerisation in emulsion polymerisation processes.
• Another object of the invention is directed to provide a simple process of making silicone emulsion having particle size up to 150 nanometer, which would reduce the total "emulsion polymerisation time" significantly.
• Another object of the present invention is directed to a process for the manufacture of silicone emulsion having particle size up to 150 nanometer which would assist faster polymer growth of the organopolysiloxane during emulsion process.
• Yet further object of the present invention is directed to making stable silicone emulsion involving standard homogenizer having particle size up to 150 nanometer by way of a selective emulsion formulation and avoiding the need for complex machinery to reduce the emulsification and polymerisation stages in such manufacture of silicone emulsion.
• a process for the manufacture of a stable emulsion having particle size (D50 value) up to 150 nanometer comprising:
• one of the critical aspects which enable obtaining of emulsion up to 150 nanometer following a simple process is the selective use of a combination of non-ionic emulsifier together with an at least one anionic emulsifier to achieve the desired particle sized emulsion.
• HLB value near to 12-15 is found to be the optimum value of the emulsifier or a mixture of emulsifiers, which help to make low particle emulsion.
• a mixture of non-ionic and anionic emulsifiers having HLB value of the mixture near to 12-15 shows optimum combinations to make low particle stable emulsion with a standard homogenizer.
• the quantity of the emulsifiers used in the above selective formulation have selective contribution to make the emulsion stable.
• the emulsion is also stabilized by use of surfactants having critical HLB values that help to make faster low particle emulsion by using standard homogenizer without need for complex ultra high pressure homogeniser.
• thermoforming of the emulsion with a temperature up to 50°C, is found to further help faster polymer growth of organopolysiloxane in the emulsion. Temperature during the emulsion preparation is found to have great importance not only to control the particle size but also control the particle size distribution and faster growth of internal phase viscosity.
• a suitable biocide is added for preventing microbial growth.
• the process uses a mixture of surfactants for making low particle organopolysiloxane by using standard homogenizer, it is important to maintain the selective formulation involving making a proper recipe of surfactants mix and recipe of organopolysiloxane and surfactants to achieve particle size up to 150 nanometer.
• one of the critical parameters include the selection of the right emulsifiers and combination of the emulsifiers to achieve the desired low particle size emulsion.
• the present invention thus achieves producing low particle emulsion in a simple way where selective emulsifier combination and temperature of emulsification and polymerisation which have a critical part to make the process simple and avoiding the use of cost extensive and complex machinery.
• the invention thus provides a process for making stable low particle emulsion from a low molecular organopolysiloxane or a mixture of organopolysiloxane.
• Organopolysiloxanes referred herein for the purpose of the invention include low molecular organopolysiloxane such as alpha omega hydroxy terminated organopolysiloxane; alpha omega alcoxy terminated organopolysiloxane; or mixture thereof.
• branched polysiloxane emulsion a tri functional or tetra functional silane or a mixture thereof is used together with above organopolysiloxanes.
• Example of R 1 in formula (I) as alkoxy groups are methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy or a phenoxy group but not limited to the said groups.
• R in formula (I) are alkyl radicals, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertbutyl, n-pentyl, isopentyl, neopentyl, tertpentyl, hexyl such as n-hexyl, heptyl, such as n-heptyl, octyl such as n-octyl and isooctyl such as 2,2,4-trimethyl pentyl, nonyl such as n-nonyl, decyl such as n-decyl, dodecyl such as n-dodecyl, octadecyl such as n-octadecyl; alkenyl such as vinyl and allyl, cycloalkyl such as cyclopentyl, cyclohex
• Organopolysiloxane used according to the present invention may be branched by way of incorporation of branching units.
• Branching units may be introduced to improve the film forming behaviour of organopolysiloxane.
• Branching unit may be trifunctional silane or tetrafunctional silane or a mixture thereof.
• Trifunctional silanes (III) and tetrafunctional silanes (IV) have the following structure: R-Si-(O-R) 3 III Si-(O-R) 4 IV
• R which may differ, is a monovalent hydrocarbon radical.
• R alkyl radicals, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl such as n-hexyl, heptyl such as n-heptyl, octyl such as n-octyl and isooctyl such as 2,2,4-trimethyl pentyl, nonyl such as n-nonyl, decyl such as n-decyl, dodecyl such as n-dodecyl, octadecyl such as n-octadecyl; alkenyl such as vinyl and allyl, cycloalkyl,
• branching units are adding during the emulsification process.
• 0.1 to 5% branching units of the emulsion is useful to make an emulsion containing organopolysiloxane having highly branched structure.
• Quantity used in the emulsion must be controlled carefully, otherwise gellation of the polymer may occur during emulsion process and emulsion destabilizes. If branched polysiloxane is not required, the silane addition is avoided.
• anionic emulsifier has an important role for simple and faster emulsion process of high internal phase viscosity emulsion having particle size up to 150 nm.
• Anionic surfactant is selected from organic sulfonic acids. Most common sulfonic acids used in the present process are alkyl aryl sulfonic acid; alkyl aryl polyoxyethylene sulphonic acid; alkyl sulfonic acid and alkyl polyoxyethylene sulfonic acid.
• R 2 which may differ, is a monovalent hydrocarbon radial having at least 6 carbon atoms.
• Most preferable R 2 groups are hexyl, octyl, decyl, dodecyl, cetyl, stearyl, myristyl, and oleyl.
• 'm' is an integer from 1 to 25.
• anionic surfactants used in the present inventions are octyl benzene sulfonic acid; dodecyl benzene sulfonic acid; cetyl benzene sulfonic acid; alpha octyl sulfonic acid; alpha dodecyl sulfonic acid; alpha cetyl sulfonic acid; polyoxyethylene octyl benzene sulfonic acid; polyoxyethylene dodecyl benzene sulfonic acid; polyoxyethylene cetyl benzene sulfonic acid; polyoxyethylene octyl sulfonic acid; polyoxyethylene dodecyl sulfonic acid and polyoxyethylene cetyl sulfonic acid.
• anionic surfactant Generally, 1 to 15% anionic surfactant is used in the present emulsion processing process. Preferably, 3-10% anionic surfactant is used in the present emulsion to get the optimum result.
• Anionic surfactant has a dual role in the present emulsion process. Anionic surfactant acts as a condensation/ring opening catalyst in together with as a surfactant for emulsion making. Thus, by using anionic emulsifier, process does not need any catalyst for polymer growth of organopolysiloxane during emulsion process.
• At least one additional emulsifier together with anionic emulsifier is essential alongwith the controlled temperature of emulsification and polymerisation for making the emulsion in a simple faster way. It is specially found by way of the present invention that at least one non-ionic emulsifier in together with anionic surfactant helps for faster simple emulsion production. Non-ionic emulsifiers having HLB value in between 10-19 are suitable to make the emulsion process simpler. Most useful surfactants of this category are polyoxyalkylene alkyl ether, polyoxyalkylene alkylphenyl ethers and polyoxyalkylene sorbitan esters.
• Some useful surfactants having HLB value in between 10-19 are polyethylene glycol octyl ether; polyethylene glycol lauryl ether; polyethylene glycol tridecyl ether; polyethylene glycol cetyl ether; polyethylene glycol stearyl ether; polyethylene glycol nonylphenyl ether; polyethylene glycol dodecylphenyl ether; polyethylene glycol cetylphenyl ether; polyethylene glycol stearylphenyl ether; polyethylene glycol sorbitan mono stearate and polyethylene glycol sorbitan mono oleate.
• Non-ionic surfactant having HLB value in-between 10-19 has a great importance in the present invention to make process more simpler.
• nonionic surfactant 1 to 25% nonionic surfactant is used in the emulsion processing process.
• 5-20% nonionic surfactant is used in the present emulsion to get the optimum result.
• Surfactant(s) having HLB value in-between 12-15 is useful to make organopolysiloxane emulsion by using standard homogenizer in shorter period and it is also well known to use a mixture of surfactants that have HLB value in-between 12-15 to get an emulsion of organopolysiloxane having long stability.
• the emulsifiers it is also important to provide selective formulation of the emulsifiers in a ratio such that the mix has HLB value preferably in-between 12-15 with at least one anionic surfactant and one non-ionic surfactant in the mixture.
• An important aspect in the present emulsion process is the selective use of a mixture of surfactants, which not only make stable emulsion in faster way by using standard homogenizer but also to produce a low particle emulsion up to 150 nm.
• Particle size of the emulsion is highly dependent on the ratio of anionic and non-ionic emulsifier (s) having HLB value of the mixture in-between 12-15.
• polymer growth rate of the orgaopolyisiloxane is also highly dependent on the particle size of the emulsion. So polymer growth rate of the organopolysiloxane during the emulsion process is much higher compared to organopolysiloxane emulsion having particle size above 150 nm.
• the temperature during the emulsion process has an important role to control the particle size of the emulsion, distribution of the particle size distribution (i.e polydispersibility, value 1 is poor and value 0.1 or less than 0.1 is very good) and polymer growth rate of the organopolysiloxane during emulsion process. It is also observed in the present emulsion process, particle size, and distribution of the particle and polymer viscosity become out of control if temperature is not maintained within a selective limit. It is found a significant deviation of final emulsion specifications take place where temperature control is not within the said selective range even though emulsion is produced by using an optimum combination of emulsifiers with a proper combination of fluid to emulsifier. Maintaining a temperature below of 50°C is useful to control the particle size, distribution of particle in the emulsion and polymer growth rate of the organopolysiloxane in the emulsion.
• emulsion temperature during the ageing of the emulsion in case of ultra high (more than 2 million mPa.s (cps)) organopolysiloxane polymer in the emulsion.
• a temperature below of 30°C is useful to make the polymerisation faster in case of ultra high organopolysiloxane polymer required in the inner phase of the emulsion.
• Emulsion polymerisation is significantly dropped if temperature is more than 30°C during ageing process, even difficult to achieve ultra high viscosity at high temperature.
• the components are homogenised by standard homogenizers.
• Useful standard shear stirring system may be used such as conventional single stage stator-rotor homogeniser or other types of standard homogeniser which are used in the normal homogenising process.
• Homogenising can be carried out in batch or continuous depend on the design of emulsion process. From the capital investment point of view, it is also clear that the process also needs a economic homogenising system and avoids the use of the expensive very high pressure homogenising system.
• the emulsion obtained following the process of the invention was highly stable.
• a study of 12 hr freeze/thaw cycles in 10°C/50°C temperature for one month also showed no creaming or separation or deformation in the emulsion.
• Emulsion particle size was measured by Malvern Zetasizer Nano - ZS. Result showed 70.3 nm particle size of the emulsion having 0.09 polydispersibility.
• a milky white emulsion was prepared by following Example I except non-ionic surfactant replaced by linear alkyl benzene sulfonic acid. Maintained temperature below 30°C like Example I and completed total emulsification process within one hr. Finally neutralized the emulsion with 85% triethanol amine and added 4 ppm Kathon CG.
• Emulsion particle size was measured by Malvern Zetasizer Nano - ZS. Result showed 168 nm particle size of the emulsion having 0.40 polydispersibility.
• a milky white emulsion was prepared by following Example I except non-ionic surfactant replaced by linear alkyl benzene sulfonic acid and did not control temperature during the emulsification process. Temperature was increased to 55°C during emulsification process and completed total emulsification process within one hr. Finally neutralized the emulsion with 85% triethanol amine and added 4 ppm Kathon CG.
• Emulsion particle size was measured by Malvern Zetasizer Nano - ZS. Result showed 185 nm particle size of the emulsion having 0.80 polydispersibility.
• a milky white emulsion was prepared by following Example I except the temperature was not maintained within the selective range during the emulsification process. Temperature was increased to 55°C during emulsification process and completed total emulsification process within one hr. Finally neutralized the emulsion with 85% triethanol amine and added 4 ppm Kathon CG.
• Emulsion particle size was measured by Malvern Zetasizer Nano - ZS. Result showed 125 nm particle size of the emulsion having 0.80 polydispersibility.
• Emulsion particle size was measured by Malvern Zetasizer Nano - ZS. Result showed 116 nm particle size of the emulsion having 0.03 polydispersibility.
• a milky white emulsion was prepared by following Example II except non-ionic surfactant replaced by linear alkyl benzene sulfonic acid. Maintained temperature below 30°C like example II and completed total emulsification process within one hr. Finally neutralized the emulsion with 85% triethanol amine and added 4 ppm Kathon CG.
• Emulsion particle size was measured by Malvern Zetasizer Nano - ZS. Result showed 185 nm particle size of the emulsion having 0.40 polydispersibility.
• a milky white emulsion was prepared by following Example II except non-ionic surfactant replaced by linear alkyl benzene sulfonic acid and did not maintain temperature as per the proposed selective range of the invention during the emulsification process. Temperature was increased to 55°C during emulsification process and completed total emulsification process within one hr. Finally Neutralized the emulsion with 85% triethanol amine and added 4 ppm Kathon CG.
• Emulsion particle size was measured by Malvern Zetasizer Nano - ZS. Result showed 235 nm particle size of the emulsion having 0.70 polydispersibility.
• a milky white emulsion was prepared as in Example II except did not maintain the temperature in the selective range as proposed under the invention during the emulsification process. Temperature was increased to 55°C during emulsification process and completed total emulsification process within one hr.
• Emulsion particle size was measured by Malvern Zetasizer Nano - ZS. Result showed 140 nm particle size of the emulsion having 0.80 polydispersibility.
• Emulsion particle size was measured by Malvern Zetasizer Nano - ZS. Result showed 117 nm particle size of the emulsion having 0.09 polydispersibility.
• a milky white emulsion was prepared by following Example III except non-ionic surfactant replaced by a mixture of 5.5 kg linear alkyl benzene sulfonic acid and 5.5 kg sodium lauryl sulphate. Maintained temperature below 30°C like example III. Then, kept the emulsion 5 hr below 25°C. Neutralized the emulsion with 85% triethanol amine after 5 hr ageing and added 4 ppm Kathon CG as a biocide. Total process including ageing was completed within six hr.
• Emulsion particle size was measured by Malvern Zetasizer Nano - ZS. Result showed 170 nm particle size of the emulsion having 0.50 polydispersibility.
• a milky white emulsion was prepared as in Example III except non-ionic surfactant replaced by linear alkyl benzene sulfonic acid and did not maintain temperature during the emulsification process. Temperature was increased to 55°C during emulsification process. Then, kept the emulsion 5 hr at 40-45°C. Neutralized the emulsion with 85% triethanol amine after 5 hr ageing and added 4 ppm Kathon CG as a biocide. Total process including ageing was completed within six hr.
• Emulsion particle size was measured by Malvern Zetasizer Nano - ZS. Result showed 230 nm particle size of the emulsion having 0.78 polydispersibility.
• a milky white emulsion was prepared by following Example III except did not maintain temperature within the selective range during the emulsification process. Temperature was increased to 55°C during emulsification process. Then, kept the emulsion 5 hr at 40-45°C. neutralized the emulsion with 85% triethanol amine after 5 hr ageing and added 4 ppm Kathon CG as a biocide. Total process including ageing was completed within six hr.
• Emulsion particle size was measured by Malvern Zetasizer NanoZS. Result showed 138 nm particle size of the emulsion having 0.80 polydispersibility.
• Emulsion particle size was measured by Malvern Zetasizer Nano - ZS. Result showed 90.5 nm particle size of the emulsion having 0.08 polydispersibility.
• a milky white emulsion was prepared by following Example IV except non-ionic surfactant replaced by linear alkyl benzene sulfonic acid. Maintained temperature below 30°C like example IV and completed total emulsification process within one hr. Finally neutralized the emulsion with 85% triethanol amine and added 4 ppm Kathon CG.
• Emulsion particle size was measured by Malvern Zetasizer Nano - ZS. Result showed 180 nm particle size of the emulsion having 0.30 polydispersibility.
• a milky white emulsion was prepared by following Example IV except non-ionic surfactant replaced by linear alkyl benzene sulfonic acid and did not maintain the temperature within the selected range under the invention during the emulsification process. Temperature was increased to 55°C during emulsification process and completed total emulsification process within one hr. Finally neutralized the emulsion with 85% triethanol amine and added 4 ppm Kathon CG.
• Emulsion particle size was measured by Malvern Zetasizer Nano - ZS. Result showed 185 nm particle size of the emulsion having 0.80 polydispersibility.
• a milky white emulsion was prepared by following Example IV except did not maintain temperature as per the selective range proposed under the invention during the emulsification process. Temperature was increased to 55°C during emulsification process and completed total emulsification process within one hr. Finally Neutralized the emulsion with 85% triethanol amine and added 4 ppm Kathon CG.
• Emulsion particle size was measured by Malvern Zetasizer Nano - ZS. Result showed 148.5 nm particle size of the emulsion having 0.80 polydispersibility.
• organopolysiloxane emulsion having particle size below is only possible to produce by simple single stage stator-rotor homogeniser when emulsifier mixture comprises at least one anionic emulsifiers and at least one non-ionic emulsifiers.
• Anionic emulsifiers or a mixture of anionic emulsifier can not produce an organopolysiloxane emulsion below 150 nm by using simple homogeniser.
• temperature control during emulsion process has an important role to control the particle size, polydispersibility of the emulsion particles and polymer growth rate.

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• 2006
  • 2006-01-26 BR BRPI0606894-4A patent/BRPI0606894B1/pt active IP Right Grant
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  • 2006-01-26 WO PCT/EP2006/000690 patent/WO2006081978A1/en not_active Ceased
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